Sudsing detergent composition



United States Patent 3,194,767 SUDSING DETERGENT CUMPGSEIHON Jim S. Berry, (Jincinnati, Ohio, assignor to The Procter 8a Gambia Company, Cincinnati, Ohio, a corporation of Qhio No Drawing. ()riginal application Dec. 18, 1961, Sier. No. 16%,231. Divided and this application Dec. 19, 1963, Ser. No. 331,916

4 Ciaims. (0. 252-462) This application is a division of copending application Serial No. 160,231, filed December 18, 1961. This invention relates to a new class of functionally substituted fluorocarbons which are analogs of corresponding functionally substituted hydrocarbons in which substantially all of the hydrogens have been replaced with fluorine. More particularly, this invention relates to a new class of highly iluorinated-alkyl amine oxide compounds.

Fluorocarbons as a class of compounds were initially developed during the early l940s. Since that time, research in the preparation of such compounds has proceeded on a rather limited basis. There are at present available commercially such fluorocompounds as the fluoroalcohols, fluorocarbon acids, and a few fiuoroolefins such as tetrafiuoroethylene.

It has now been discovered that certain new functionally substituted fi-uorocarbons may be produced which have exceptional and unexpected properties. Accordingly, it is an object of this invention to provide new compositions of matter. A further object is to provide a novel class of perfluorinated functionally substituted corn-pounds. Another object is to provide a class of perfiuorocarbon amine oxide compounds having surface active and detergent properties. A further object is to produce a new class of perfluorocarbon amine oxide compounds which have outstanding sudsing properties when employed in detergent compositions. Still another object of this invention is to provide a new class of perfluorocarbon amine oxide compounds which possess the property of rendering fabrics treated therewith to be highly lipid repellent. A further object is to provide a series of new compounds such as N,N-dimethyl-1,l-dihydrogen perfiuorooctyl amine oxide, N,N-dimethyl-l,l-

' dihydrogen perfluorodecyl amine oxide and N,N- dimethyl-l,l-dihydrogen perfluoroundecyl amine oxide. Another object is to produce novel compositions containing the newly discovered class of perfluorocarbon amine oxide compounds.

The class of compounds covered by this invention conforms to the following general formula,

R;CH N(O)RR" ethyl, and n-propyl.

The nitrogen-oxygen linkage represented by the arrow @lhflbl. Patented July 13, 196% in the structural formula is variously called a coordinatecovalent bond, dative bond, or semipolar link and represents a single pair of electrons, both of which come from the nitrogen donor atom.

The compounds of this invention, in general, can be prepared by a multi-step process in which the starting material is a peifluoroalkyl carboxylic acid. The process generally conforms to the following broad outline.

Initially a perfluoroalkyl carboxylic acid is esterified by a lower alcohol in the presence of a small amount of a mineral acid catalyst. The resulting ester is then separated and dissolved in dry ether into which anhydrous ammonia is passed at ice bath temperatures, e.g.,'

0 to 5 C., until a strong ammonia odor is observable. After evaporation of the ether and the ammonia, the product is recovered as an amide.

The next stage involves dehydration of the amide to produce a nitrite by heating the amide derivative in the presence of a dehydrating agent. Thereafter, the nitrile is reduced by the introduction of hydrogen at moderately high pressure. After filtration and twofold distillation, the 1,-l-dil1ydr-ogen-perfiuoroalkyl amine is recovered.

Allcylation of the primary amine to a tertiary amine is then accomplished in any conventional manner. For example, rnethylation can be carried on by refluxing a mixture of the primary amine :produced by the preceding step, a small amount of a concentrated mineral acid, formic acid, and formaldehyde. After a considerable reflux period, the mixture is neutralized by being poured into an excess of base solution, dried, and distilled. On analysis, the product is N,N-dimethyl-1,l-dihydrogen-perfluoroalkyl amine.

By the next step, this compound is oxidized by show ing the tertiary amine to react with 30% hydrogen peroxide and glacial acetic acid and heating to about to C. with occasional stirring for about 2 hours. The mixture is evaporated, solvent is removed, and the semisolid residue is dried in vacuo for about 24 hours. The sample is pulverized, triturated with dry ether, and filtered to give the N,N-dimethyl-1,1-dihydrogen perfluoroallcyl amine oxide.

Perfiuoroalkyl carboxylic acids from which members of this new group of compounds may be produced and methods for their preparation are disclosed by Simons in his treatise, Fluorine Chemistry, volumes I-IV, Academic Press, New York, 1950. Such methods are usually referred to as the electrochemical methods of fluorination and, very briefly, comprise dissolving organic substances such as carboxylic acids in anhydrous hydrogen fluoride to give conducting solutions. Direct electric current at a low voltage is passed through such a solution, or through a suspension of an insoluble organic compound in hydro-gen fluoride made conducting by the addition of an electrolyte, causing hydrogen to be evolved at the cathode and the organic material to be fi-uorinated.

In order to illustrate a preferred method for prepar ing the compounds of the invention, but without being limited thereto, the following example is given.

E) lAMPLE.-N,N-DIl\lETl-IYL-l l-DIHYDROGEN- PERFLUOROOCTYLAMINE OXIDE 75 grams of perfluorooctanoic acid, C7F15COOH, was added to 22 grams of concentrated sulfuric acid and 12 grams of methanol. The mixture was stirred for approximately 2 hours at about 100 C. There was thus produced an ester, methyl pertluorooctanoate, CI7F15 CO CH This was purified by water washing, drying, and distilling, and had a boiling point of about 158 C., and was obtained in a yield of 79%.

30 grams of the methyl perfiuorooctanoate was dissolved in about 100 ml. of dry ethyl ether. The mixture was stirred while anhydrous ammonia was passed in at ice bath temperatures (5 C.) until a strong ammonia odor was observed. The ether and the ammonia were evaporated, and the dry amide product so produced was purified by being dissolved in a 50% benzene-50% acetone solution and recrystallized, yielding 81% of perflu-orooctanamide having a melting point of 143- 144" C.

38 grams of the perfiuorooctanamide and 62.5 grams of phosphorous pentoxide were then heated together in a distilling flask at a temperature of about ZOO-210 C. until no further distillate was obtained. The product 1 heavy-duty detergency evaluations. This was completely unexpected in view of the relatively short fluorocarbon chain lengths of the new compounds as compared to the well known C to C hydrocarbon chains in compounds having known detergency properties.

The test methods employed the Well-known Terg-O- Tometer machine which is described in the literature, for example, in Detergency Evaluation and Testing, by J. C. Harris, published by Interscience Publishers, Inc., 1954. Sample washing formulations were prepared containing of the detergent compound being tested, 50% of sodium tripolyphosphate, and of sodium sulfate. Carefully prepared soiled swatches, each containing equal amounts of a standard soil, were then washed in the prepared sample solutions and cleaning results determined by measuring the light reflectance of the washed swatches as well as measuring the residual so formed was perfiuoroheptylcyanide, C F CN, atv

yields of 82%. This nitrile derivative had a boiling point of 102 C. at atmospheric pressure.

A mixture of 29.6 grams of previously formed perfiuoroheptylcyanide, 400 milligram-s of an Adams platinum catalyst, and 75 ml. of absolute ether were placed in an autoclave into which hydrogen was introduced until a pressure of 1500 p.s.i. was reached. Reduction by the hydrogen was continued for about 2 hours at temperatures of about 55C. to about 60 C. This was followed by filtration and two distillations of the autoclave contents producing 80% of a primary amine which was 1,1-dihydrogen-perfluorooctyl amine, CqF15CH2NH2, and which had a boiling point of about 149l50 C.

The primary amine was converted to a tertiary amine by methylating in the following manner. A homogeneous single phase aqueous solution was formedby mixing 24.8

grams of 1,1-dihydrogen perfiuorooctylamine and 6.3-

ml. of concentrated hydrochloric acid and this mixture was combined with 39.9 grams of 90% formic acid and 36.4 grams of formaldehyde solution. The mixture was refluxed for approximately 19 hours and then poured into excess 25% sodium hydroxide solution to neutralize the mixture. mixture with ethyl ether and the aqueous layer Was discarded. The ether layer was washed with water, dried over sodium hydroxide, and then distilled. The resulting product was N,N-dimethyl-1,l-dihydrogen-perfiuorooctylamine, C F CI-I N(CH boiling at 161 C., having a refractive index, n of 1.3134 and d of 1.542, and was produced in a yield of 83% The tertiary amine was thereafter oxidized to the amine oxide by combining 15.0 grams of N,N-dirnethyl-1,1-dihydrogen-perfluorooctylamine, 15 ml. of 30% aqueous hydrogen peroxide, and 15 m1. of glacial acetic acid.

and heating at 7 580 C. with stirring for about 2 hours.

After removal of solvent in vacuo, the semisolid residue Detergency As a generalization it was discovered that functionally substituted fiuorocarbons as a class of compounds act poorly in detergency. The only notable exceptions are the perfluorocarbon amine oxides produced by this invention, which gave rather surprisingly good results in The amine product was extracted from the were as follows.

soilafter a washing treatment. These tests. showed the heavy-duty detergency of the perfluorocarbon amine oxide compounds to be comparable to sodium alkyl benzene sulfonate wherein. the alkyl radical is a propylene tetramer.

Sudsing The perfluorocarbon aminev oxides of, this invention were discovered to be clearly outstanding in sudsing prop erties and uniquely excellent in their capacity to produce suds even in the presence of heavy soil loads. Moreover, tests showed that the perfluorocarbon amine oxides, e.g., N,N-dirnethyl-1,l-dihydrogen perfiuorooctylamine oxide of theexample, can also function as excellent suds builders for relatively low sudsing compounds such. as C -C alkyl benzene sulfonates.

' Sudsing performance of detergent surfactant compoundscan be very important. For example, in a product designed for dishwashing and heavy-duty laundry detergency, good initial sudsing and suds which last a long time are important, because the housewife and other users generally have come to associate sudsing with cleansing action and to consider the presence ofsuds as an indicator of the presence of active detergent.

' The test used to measure the sudsing propensity of the compounds of this invention and detergent compounds with which they are compared may be characterized as a suds plunger test which simulates a conventional. Washing situation. The test consisted principally of preparing an aqueous solution containing a standardized soil load and placing the solution into a metal cylinder. A measured amount of a detergent formulation containing the compound to be tested for sudsing capacity was added to the solution in the cylinder and the .solution was then vigorously agitated for astandardized period of time by means of a vertically actuated plunger. The suds height measured in millimeters was read and recorded. The stabilityof theysuds producedwas determined by allowing the column of suds to remain undisturbed for a few minutes and then taking a second reading. Any marked decrease in the height of the suds column would indicate I that the suds produced would not be of an enduring nature.

The foregoing, described test provides a dependable method for determining the relative sudsing capacity of various compounds as well as the stability of the suds produced. The data" set forth'below in Table I were obtained pursuant to the above test, and it establishes the perfluorocarbon amine oxides of this invention as outstanding sudsing materials. .The specific test conditions The temperature of the solution was F. the concentration of the detergentformulation in the solution was 0.15% by weight, the pHwaslO, and

the water was of '7 grains per gallon hardness. The'test formulation consisted of 17.5% organic detergent surfactant being tested for sudsing, 50% sodium tripolyphosphate, 23% sodium sulfate, 6% sodium silicate, and

6 tion, the suds built with such amine oxides were found to be exceptionally stable.

Mildness tests The fluorocarbon amine oxides, especially the bLN-dimethyl-1,1-dihydrogen perfluorooctylamine oxide of the Soil emulsion load in grams per liter Sodium perfluorooetanoate C 10 g a. 4.0 2.0 0.0 0.0 0.0 0.0 0.0 Sodium 1,1-dihydrogen perfiuorooctyl sulfate (C F1 CH OSOaNa) 8.0 4.0 0.0 0.0 0.0 0.0 0.0 Alkyl benzene sulionate 114.0 9.7 5.0 2.5 0.0 0.0 0.0 N,N-dirnethyl-1,1-dihydrogen perfluorooctyl amine oxide 114.0 112.5 112.0 110.0 100.8 91.0 73.0

The above table indicates that both sodium perfiuoroexample, are extremely mild to the skin. Moreover, they octanoate, C F CO Na, and sodium-1,1-dihydrogen-perfluorooctyl sulfate, C F Ci-I OSO Na, were unable to produce any measurable suds in the presence of a soil load of between 0.3 gram and 0.6 gram per liter. The alkyl benzene sulfonate only produced a negligible amount of suds in the presence of a soil load of about 0.9 gram. At 1.2 grams, the alkyl benzene sulfonate produced no measurable suds. The perfluorocarbon amine oxide, however, maintained its exceptionally high capacity for suds production at soil loads as high as 1.8 grams per liter. This capacity to produce profuse amounts of suds even under relatively high soil loads renders the compounds suitable for applications wherein high soil loads might be encountered, as, for instance, dishwashing and heavy-duty detergency. Moreover, the suds produced by the amine oxide compound were exceptionally stable. A reading taken a short while after the initial suds height reading indicated that the suds columns produced by the perfiuorinated amine oxides had not noticeably decreased in suds height, attesting to the stability of the suds produced. Each of the other column heights had substantially lower readings, indicating that the suds produced were less stable than those produced by the perfluorinated amine oxide compound.

As mentioned above, the compounds of this invention also function very well as suds builders for relatively poor sudsing detergent compounds. One such low sudsing compound is the alkyl benzene sulfonate employed in the preceding test. Suds builder capacity of the perflucrinated amine oxide compounds was observed from repeating the same test procedures used to measure sudsing capacity. First the suds heights were recorded for a formulation containing alkyl benzene sulfonate as the organic detergent surface active agent. Then the formulation was modified to include a small amount of a compound of this invention. The specific formulation used consisted of 17.5% sodium alkyl benzene sulfonate, 50% sodium tripolyphosphate, 23.0% sodium sulfate, 6.0% sodium silicate, and 3.5% of N,N-dimethyl-l,l-dihydrogen perfluorooctyl amine oxide as a suds builder. The results are produced in the following table.

TABLE II.SUDS BUILDING CAPACITY [Column height in millimeters] function as effective mildness additives for other organic detergent surfactant materials which may be less mild. An example of such an organic material is the same alkyl benzene sulfonate employed in each of the preceding evaluations.

The exceptional mildness of the compounds of this invention was determined by conducting Guinea Pig Imrnersion Tests. in these tests groups of three guinea pigs which had their abdomens shaved were immersed up to the thorax in an aqueous solution of the detergent surfactant compounds being tested. The bath was maintained at a constant temperature of about 37 (3., and the immersion periods were for 4 /2 hours at the same period of time on each of three consecutive days. The readings were made about 72 hours after the conclusion of the third exposure.

TABLE III.GUINEA PIG IMNEERSION TEST The skin grade values assigned are based on a range of 1 to 10 within which values of '1 and 2 represent severe degrees of skin irritation. A value of 1 represents the most extreme irritation of the skin. With guinea pigs a value of 1 indicates bleeding and skin fissures, While a value of 1 in exaggerated tests on human subjects indicates severe redness and dryness of the skin. Thus the exaggerated exposure tests on animals are much more extreme than comparable tests conducted on human subjects. Intermediate values going from 4 to 8 represent increasing mildness. Values of 9 and 10, such as those achieved Soil emulsion load in grams per liter These data show the marked relative ability of the perfluorinated amine oxide substantially to build the sudsing capacity of alkyl benzene sulfonate solutions.

by the N,N-dimethyl-1,l-dihydrogen perfluorooctylamine oxide and a LIZ-mixture respectively of N,N-dimethyl-1,1- dihydrogen perfiuorooctylamine oxide and the alkyl ben- In addi- 75 zene sulfonate, represent the ultimate in mildness.

Effect on fabrics A very important and valuable property of the perfluorocarbon amine oxides of this invention is the ability of these materials to produce surfaces on fabrics which are highly repellent to lipids. This property was discovered by conducting the following test. Muslin swatches were dipped into a 2.4 l M aqueous solution of the compound to be tested, the excess was shaken off, and then the muslin swatch was air dried. Thereafter, an assorted number of lipids were separately added dropwise onto the treated swatches and the length of time it took for the droplet to penetrate the swatch was noted. While other factors such as surface roughness of the fabric, viscosity, and surface tension of the lipid may have a bearing on the penetration or wetting time, the tests are highly dependable for determining the relative value of lipid repellency of a treated swatch. The test results tabulated below in Table IV are classified into categories such as .immediate penetration, slow penetration, etc.

such as, for example; the substitution of various perfluorocarboxylic acid starting materials. Since the selection of he pertluorocarboxylic acid will determine the perfiuorocarbon chain length, it may. be varied'at will depending on the product desired. The specific" reaction conditions such as temperatures, pressures, etc, may have to be adjusted to accommodate different starting materials,

but these variations in the exemplified method will be readily apparent to persons skilled in the art.

In those instances where the N,N-dialkyl radicals are to be mixed alkyls such as N-ethyl, N-n propyl, etc., the

' tertiary amine may be formed by introduction of the alkyl groups to the l,1-dihydrogen-perfluoroalkyl amine by the well known Hofmann procedure, for example. This procedure is described, for instance, in N. V. Sidgwicks Organic Chemistry of Nitrogen, Oxford University Press, 1937, pp. 13-14. g

The sudsing, mildness, and detergency properties as well as the effects on fabrics caused by these additional TABLE IV.RATE OF -WETTING- 1 Nujol Methyl Methyl Dimethyl Muslin swatch sample containing about Cotton- (liquid palmiundecyl dodeeyl Dodeeyl Dibutyl Lauryl 1% by wt. level of following agent seed oil lpetroi tate ketone amme amine amine alcohol cum 1 Untr T m I mm x Tmm Tmm Imm Imm- Imm 1mm. 2 N,N-dimethyl-l,l-dihydrogen per- Non- Non- Non Slow- Slow Slowz.-. Slow. Slow.

fiuorooetyl amine oxide. wetwe twetting. ting. ting. 3 Tetrapropylene benzene sulionat Fast Fast Imm Imm. mm T Tmm Imm. 4...- Stfraight chain dodeeyl benzene suldo do Tmm Tmm Tmm mm T m Imm.

onate.

1 Imm.=few seconds; iast=up to 2 min.; slow=2-15 min.; non-wetting=more than 1 hour.

vention were capable of imparting to fabrics a marked softening effect. This was very surprising because here-' tofore this phenomenon has been associated generally with cationic surface active agents having about 18 carbon atoms in the hydrophobic chain. The test used to reveal this softening effect comprised uniformly wetting a terry cloth :swatch with a solution containing a measured concentration of the compound being tested and allowing the swatch to dry. The N,N-dirnethyll,l-dihydrogen perfiuorooctylamine oxide gave detectable softening of terry cloth swatches at levels as low as 0.05% of the fabric weight.

Examples of other perfiuorocarbon amine oxides which are contemplated as being produced according to this invention and thus within the scope thereof include (1) N,N-diethyl-1,1-dihydrogen perfluorobutyl amine oxide. (2) N,N-di-n-propyl-1,1-dihydrogen perfiuoroamyl amine oxide. I (3) N-methyl-N-ethyl-l, l-dihydrogen perfluorohexyl amine oxide.

(4) N-methyl, N-n-propyl-l,l-dihydrogen perfiuoroheptyl H compounds are comparable to those described above for N,N-dimethyl-l,l-dihydrogen perfluorooctylamine oxide and can generally be substituted freely in place thereof.

Compounds of this invention are useful per se as detergents and surface active agents. Desirably they are used with other materials to form detergent compositions, particularly solid compositions as, for example, bar, flake or granular compositions. Such detergent compositions can contain from about 5% to about 80% of the perfluorocarbon amine oxides of this invention andfrom about 20% to about 95% of anionic organicdetergents'nonionic detergents, water-soluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts, or mixtures thereof. Granular or flake detergents preferably contain about 5% to about 50% of the perfluorocarbon amine oxides of this invention.

Anionic organic detergents used alone or in admixture in combination with the compounds of this invention include both the soap and the non-soap detergents. Examples of suitable soaps are the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of anionic organic non-soap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates; alkyl monoglyceride' sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters ofisethionates; alkyl phenol polyethenoxy sulfonates. In these compounds the alkyl and acyl groups, respectively,

contain 10 to 20 carbon atoms. They are used in the form amples are: sodium lauryl sulfate; potassium N-methyl lauroyl' tauride; triethanolarnine dodecyl benzene sulfo- *nate;

The examples of nonionic organic detergents are: polyethylene oxide condensates of alkyl phenolswherein the alkyl group contains from 6 to 12 carbon atoms (e.g., octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkyl phenol in the range of 10:1 to 25: 1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges from 5,000 to 11,000; the condensation products of from about to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms (e.g., lauryl alcohol).

Water-soluble inorganic alkaline builder salts used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, monoand disodium orthophosphate, and potassium bicarbonate. Such inorganic builder salts enhance the detergency of the subject perfiuorocarbon amine oxides.

Examples of water-soluble organic alkaline sequestrant builder salts used alone or in admixture are alkali metal amino polycarboxylates; e.g., sodium and potassium ethylene diamine tetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates and sodium and potassium N- (2-hydroxyethyl)-nitrilo diacetates. Mixed salts of these polycarboxylates are also suitable. The alkali metal salts of phytic acid, e.g., sodium phytate, are also suitable as organic alkaline sequestrant builder salts (see US. Patent 2,739,942).

Preferred detergent compositions contain about 7% to about 50% of the perfluorocarbon amine oxides of this invention and about an 8%75% amount of sodium tripolyphosphate. Particularly preferred amine oxides are lLN-dimethyl-l,l-dihydrogen p-erlluorooctylamine oxide, N,N-dimethyl-1,l-dihydrogen perfiuorononyl amine oxide and N,N-dimethyl-1,l-dihydrogen perfluorodecyl amine oxide, all of which have valuable sudsing and lipid repellent characteristics.

When the perfiuorocarbon amine oxides of this invention are employed as suds builders for low-sudsing detergent compounds, they may be present in the weight ratio of amine oxide to low-sudsiug detergent compound of about 1:1 to about 1:6. A more preferred ratio is 1:2 to about 1:5. The data presented in Table II, for example, were reported from tests using a ratio of amine oxide to sodium alkyl benzene sulfonate of 1:5.

Generally, any low-sudsing organic detergent compound may be built by the perfiuorocarbon amine oxides of this invention.

The detergent compositions of this invention may conit tain any of the usually employed adjuvants, diluents, and additives without adversely affecting the basic properties of the new compositions. For example, ampholytic detergents, cationic detergents, perfumes, antitarnishing agents, antidedeposition agents, bacteriostatic agents, dyes, pigments, tluorescers, and the like are contemplated.

As many apparently widely diiferent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the invention is not limited to the specific embodiments thereof except as defined by the appended claims.

What is claimed is:

1. A detergent composition consisting essentially of a relatively low sudsing detergent compound and as a suds builder an effective amount of a member of the class of compounds having the following formula wherein R represents a perfluorinated straight chain alkyl radical ranging from C F to C F and R and R" represent lower alkyl radicals selected from the group consisting of methyl, ethyl and n-propyl, and wherein the ratio of said suds builder to said detergent compound is from about 1:1 to about 1:6 by weight.

2. The detergent composition of claim 1 wherein the suds builder is selected from the group consisting of N,N dimethyl-1,1-dihydrogen perfluorooctyl amine oxide, N,N- dimethyLLl-dihydrogen perfluorononyl amine oxide, N, N-dimethyl-1,1-dihydrogen perfiuorodecyl amine oxide.

3. The detergent composition of claim 1 wherein the low sudsing detergent compound is an alkyl benzene sulfonate.

4. The detergent composition of claim 1 wherein the ratio of said suds builder to said detergent compound is from 1:2 to 1:5.

References Cited by the Examiner UNITED STATES PATENTS 2,169,976 8/39 Guenther et al 260583 2,999,068 9/61 Pilcher et al 252l52 XR 3,G0l,945 9/61 Drew et al 252--152 3,047,579 7/62 l/Vitman 260-584 XR 3,085,982 4/63 Steer et al 252-137 JULIUS GREENWALD, Primary Examiner.

ALBERT T. MEYERS, Examiner. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A RELATIVELY LOW SUDSING DETERGENT COMPOUND AND AS A SUDS BUILDER AN EFFECTIVE AMOUNT OF A MEMBER OF THE CLASS OF COMPOUNDS HAVING THE FOLLOWING FORMULA 